US11492441B2 - Blocked isocyanate, photo-curable composition, resin, and method of manufacturing three-dimensional object - Google Patents
Blocked isocyanate, photo-curable composition, resin, and method of manufacturing three-dimensional object Download PDFInfo
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- US11492441B2 US11492441B2 US16/190,637 US201816190637A US11492441B2 US 11492441 B2 US11492441 B2 US 11492441B2 US 201816190637 A US201816190637 A US 201816190637A US 11492441 B2 US11492441 B2 US 11492441B2
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/81—Unsaturated isocyanates or isothiocyanates
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- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
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- B33Y70/00—Materials specially adapted for additive manufacturing
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a blocked isocyanate, a photo-curable composition, a resin, and a method of manufacturing a three-dimensional object.
- Stereolithography involving curing a liquid photo-curable composition with light, such as an ultraviolet ray, layer by layer and laminating the layers sequentially to produce a desired three-dimensional object has been extensively investigated.
- the applications of the stereolithography are not exclusive to creation of a prototype (rapid prototyping) for shape confirmation, and have extended to, for example, creation of a working model or a mold (rapid tooling) for functional verification.
- the applications of the stereolithography are extending also to creation of an actual product (rapid manufacturing).
- a related-art photo-curable composition such as a urethane-acrylate photo-curable composition
- the photo-curable composition has a problem in that toughness is reduced when stiffness or strength is to be increased.
- an object of the present invention is to provide a photo-curable composition capable of creating a three-dimensional object excellent in both of: stiffness and strength; and toughness.
- a 1 to A 4 each independently represent a structure represented by the following general formula (2), and B represents a structure represented by the following general formula (3);
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- L 1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- R 3a , R 3b , R 4 , R 5 , R 6 , and R 7 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
- Y 1 represents a divalent linking group
- “a” represents an integer of 1 or more and 99 or less.
- a photo-curable composition for creating a three-dimensional object capable of creating a three-dimensional object having higher toughness than in the related-art can be provided.
- FIG. 1 s a view for schematically illustrating a reaction scheme in which a photo-curable composition according to an embodiment of the present invention is irradiated with light to be cured, and is then subjected to heat treatment.
- a blocked isocyanate according to this embodiment is a blocked isocyanate represented by the general formula (1):
- a 1 to A 4 each independently represent a structure represented by the following general formula (2), and B represents a structure represented by the following general formula (3);
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- L 1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- R 3a , R 3b , R 4 , R 5 , R 6 , and R 7 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
- Y 1 represents a divalent linking group
- “a” represents an integer of 1 or more and 99 or less.
- the blocked isocyanate is a (meth)acrylic compound having at least four (meth)acryloyl groups.
- the “(meth)acryloyl group” as used herein means an acryloyl group or a methacryloyl group
- the “(meth)acrylic compound” as used herein means an acrylic compound or a methacrylic compound.
- the (meth)acryloyl group is a polymerizable functional group
- the blocked isocyanate is subjected to a polymerization reaction through a radical generated from a photo-radical generator described below.
- the substituent may be a substituent including a carbon atom.
- an atom of the substituent which is bonded to each of L 1 , R 2 , R 3a , R 3b , R 4 , R 5 , R 6 , and R 7 is an atom other than the carbon atom.
- the number of carbon atoms included in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.
- R 2 preferably represents a group selected from the group consisting of a tert-butyl group, a tert-pentyl group, and a tert-hexyl group.
- a temperature (deblocking temperature) at which a photo-curable composition having been photo-cured is subjected to heat treatment to be deblocked can be reduced.
- the blocked isocyanate can be synthesized easily.
- the blocked isocyanate can be synthesized at low cost.
- L 1 preferably represents an ethylene group or a propylene group from the viewpoints of easy availability and easy synthesis.
- Y 1 preferably represents at least one divalent linking group selected from the group consisting of groups represented by the following formulae (B1) to (B3) from the viewpoints of easy availability and easy synthesis.
- a 1 to A 4 are preferably identical to one another. That is, the blocked isocyanate is preferably represented by the following general formula (I). With this, the blocked isocyanate can be synthesized easily at low cost.
- A represents a group represented by the general formula (2)
- B represents a group represented by the general formula (3).
- blocked isocyanates represented by the following formulae (I-1) to (I-21).
- the synthesis method for the blocked isocyanate includes a step (I) and a step (II) described below.
- This step is a step of subjecting a polyol and a diisocyanate to a reaction. With this, a tetraisocyanate having a polyol skeleton is obtained.
- the polyol to be used in this step is a compound having hydroxyl groups at both ends of a polymer.
- examples thereof include, but are not limited to, a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polyacetal. Those polyols may be used as a mixture thereof.
- the polyol preferably has a number average molecular weight Mn of 100 or more and 5,000 or less.
- Mn number average molecular weight
- the molecular weight of the finally obtained blocked isocyanate is reduced.
- the polyol has a number average molecular weight Mn of more than 5,000, the molecular weight of the finally obtained blocked isocyanate is increased.
- a curable composition is increased in viscosity, and thus operability is reduced, or the photo-cured/thermally cured product described below is reduced in modulus of elasticity.
- diisocyanate to be used in this step examples include, but are not limited to: aliphatic diisocyanates, such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic diisocyanates, such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), methylenebis(cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, and norbornane diisocyanate; and aromatic diisocyanates, such as phenylene diisocyanate, tolylene diis
- the polyol and the diisocyanate are preferably subjected to a reaction in a solvent.
- the solvent is not particularly limited as long as the polyol and the diisocyanate are dissolved therein. Specific examples thereof include: dialkyl ethers, such as diethyl ether and dipropyl ether; cyclic ethers, such as 1,4-dioxane and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, diisopropyl ketone, and isobutyl methyl ketone; esters, such as methyl acetate, ethyl acetate, and butyl acetate; hydrocarbons, such as toluene, xylene, and ethylbenzene; halogen-based solvents, such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroe
- the ratio is less than 4
- a ratio of a diisocyanate is increased as compared to a ratio of a target tetraisocyanate having a polyol skeleton, and the yield of the target tetraisocyanate is reduced.
- the ratio is more than 20
- the diisocyanate which is a raw material, remains unreacted excessively after the reaction, and it becomes difficult to remove the unreacted diisocyanate in some cases.
- This step is preferably performed in an inert atmosphere, such as nitrogen, helium, or argon. In addition, this step is performed at preferably 10° C. or more and 150° C. or less, more preferably 40° C. or more and 100° C. or less. In addition, this step may be performed under reflux. When this step is performed at a reaction temperature of more than 150° C., there is an increased risk of occurrence of a side reaction. When this step is performed at a reaction temperature of less than 10° C., a reaction speed is reduced, and hence a reaction time period is prolonged or the yield is reduced.
- an inert atmosphere such as nitrogen, helium, or argon.
- this step is performed at preferably 10° C. or more and 150° C. or less, more preferably 40° C. or more and 100° C. or less.
- this step may be performed under reflux.
- this step is performed at a reaction temperature of more than 150° C., there is an increased risk of occurrence of a side reaction.
- This step may be performed under the presence of a catalyst.
- the catalyst include: organic tin-based compounds, such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate, and tin 2-ethylhexanoate; naphthenic acid metal salts, such as copper naphthenate, zinc naphthenate, and cobalt naphthenate; and tertiary amines, such as triethylamine, benzyldimethylamine, pyridine, N,N-dimethylpiperazine, and triethylenediamine.
- Those catalysts may be used alone or in combination thereof.
- the amount of the catalyst to be used may be 0.001 mass % or more and 1 mass % or less with respect to 100 mass % of a total amount of the polyol.
- the tetraisocyanate having a polyol skeleton obtained by this step may be separated and purified by a conventional separation method involving, for example, separation means, such as reprecipitation with a poor solvent, concentration, or filtration, or combination separation means thereof.
- This step is a step of subjecting a blocking agent and the tetraisocyanate having a polyol skeleton obtained by the step (I) to a reaction. With this, the blocked isocyanate according to this embodiment is obtained.
- blocking agent refers to a compound which can react with an isocyanate group (—NCO) of the tetraisocyanate to protect the active isocyanate group.
- the isocyanate group protected with the blocking agent is called a blocked isocyanate group.
- the blocked isocyanate group, which is protected with the blocking agent, can be kept stable under a normal state.
- the blocking agent dissociates from the blocked isocyanate group (deblocking), and the original isocyanate group can be regenerated.
- the blocking agent to be used in this step is not particularly limited as long as the blocking agent is a (meth)acrylic compound having an amino group, but is preferably a compound selected from tert-butylaminoethyl (meth)acrylate, tert-pentylaminoethyl (meth)acrylate, tert-hexylaminoethyl (meth)acrylate, and tert-butylaminopropyl (meth)acrylate.
- a deblocking temperature of the blocked isocyanate can be reduced.
- the blocking agent and the tetraisocyanate having a polyol skeleton are preferably subjected to a reaction in a solvent.
- the solvent is not particularly limited as long as the blocking agent and the tetraisocyanate having a polyol skeleton are dissolved therein.
- the solvents described in the step (I) may be used.
- This step is preferably performed in an inert atmosphere, such as nitrogen, helium, or argon.
- this step is performed at preferably 0° C. or more and 150° C. or less, more preferably 50° C. or more and 100° C. or less.
- this step may be performed under reflux.
- this step is performed at a reaction temperature of less than 0° C., the reaction is difficult to proceed.
- this step is performed at a reaction temperature of more than 150° C., there is a risk in that the blocking agents are polymerized with each other through a polymerization reaction between (meth)acryloyl groups. As a result, there is a risk in that the yield is reduced.
- This step may be performed under the presence of a catalyst.
- a catalyst As specific examples of the catalyst, the catalysts described in the step (I) may be used.
- a polymerization inhibitor may be used for the purpose of suppressing the polymerization between (meth)acryloyl groups of the blocking agents.
- a polymerization inhibitor may be used for the purpose of suppressing the polymerization between (meth)acryloyl groups of the blocking agents.
- Specific examples thereof include benzoquinone, hydroquinone, catechol, diphenyl benzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, dibutylhydroxytoluene, and phenothiazine.
- the blocked isocyanate obtained by this step may be separated and purified in the same manner as in the step (I).
- a photo-curable composition according to a second embodiment of the present invention is described.
- the photo-curable composition according to this embodiment includes: a blocked isocyanate (a) according to the first embodiment; a chain extender (b); and a photo-radical generator (c).
- the blocked isocyanate (a) the blocked isocyanate described in the first embodiment is used.
- the blocked isocyanate (a) to be included in the photo-curable composition one kind or a plurality of kinds of blocked isocyanates may be included.
- the blending ratio of the blocked isocyanate (a) in the photo-curable composition is calculated based on a total mass of the plurality of kinds of blocked isocyanates.
- the blending ratio of the blocked isocyanate (a) in the photo-curable composition is preferably 5 mass % or more and 90 mass % or less, more preferably 10 mass % or more and 70 mass % or less with respect to the entirety of the photo-curable composition.
- the blending ratio is less than 5 mass %, a photo-cured product and a photo-cured/thermally cured product described below are reduced in modulus of elasticity and toughness.
- the photo-curable composition is increased in viscosity, and its handling becomes difficult.
- the chain extender (b) is a compound having, in a molecule thereof, at least two active hydrogens, which each react with an isocyanate group to be generated through deblocking of a blocked isocyanate group of the blocked isocyanate (a).
- the chain extender (b) preferably includes a compound having, in a molecule thereof, at least two functional groups selected from the group consisting of a hydroxyl group, an amino group, and a thiol group.
- the chain extender (b) more preferably includes at least one selected from the group consisting of a polyol having at least two hydroxyl groups, a polyamine having at least two amino groups, and a polythiol having at least two thiol groups.
- the chain extender (b) has a number average molecular weight Mn of preferably 1,000 or less, more preferably 500 or less.
- Mn number average molecular weight
- the chain extender (b) can efficiently react with the isocyanate group to be generated through deblocking when the photo-curable composition having been photo-cured is subjected to heat treatment as described below.
- chain extender (b) may include: linear diols, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; diols each having a branched chain, such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl
- a ratio of the number of moles of the chain extender (b) to the number of moles of the blocked isocyanate (a), (number of moles of the chain extender (b)/number of moles of the blocked isocyanate (a)), is preferably 0.5 or more and 5 or less, more preferably 2 or more and 4 or less.
- the ratio is less than 0.5, there are tendencies that the efficiency of the reaction between the isocyanate group and the chain extender (b) is reduced, and various mechanical characteristics of the photo-cured product and the photo-cured/thermally cured product described below are reduced.
- the ratio is more than 5
- the chain extender (b) remains unreacted excessively in a three-dimensional object, and various mechanical characteristics of the photo-cured product and the photo-cured/thermally cured product described below are reduced.
- the photo-radical generator (c) is a compound which generates a radical serving as a polymerization factor when irradiated with an active energy ray, such as light having a predetermined wavelength.
- the photo-radical generator (c) may be a compound which is decomposed to generate a radical when irradiated with an active energy ray.
- the photo-radical generator is a photo-polymerization initiator which generates a radical when irradiated with an active energy ray, such as light (e.g., an infrared ray, visible light, an ultraviolet ray, a far-ultraviolet ray, an X-ray, a charged particle beam, such as an electron beam, or radiation).
- photo-radical generator (c) examples include, but are not limited to: carbonyl compounds, such as benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzil, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methyl phenylglyoxylate, ethyl phenylglyoxylate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds, such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; and acylphosphine oxides, such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide.
- carbonyl compounds such as benzoin, benzoin monomethyl ether, benzoin isopropyl ether,
- Examples of commercially available products of the photo-radical generator include, but are not limited to: IRGACURE series, such as IRGACURE 184 and IRGACURE 819, and DAROCUR series, such as DAROCUR 1173 and DAROCUR TPO (all of which are manufactured by BASF); and KAYACURE series, such as KAYACURE DETX-S and KAYACURE CTX (all of which are manufactured by Nippon Kayaku Co., Ltd.).
- the addition amount of the photo-radical generator is preferably 0.05 mass % or more and 20 mass % or less, more preferably 0.1 mass % or more and 5 mass % or less when the total amount of the photo-curable composition is defined as 100 mass %.
- the addition amount is less than 0.05 mass %, the radical to be generated becomes insufficient, and the polymerization conversion rate of the photo-curable composition is reduced. As a result, the strength of the photo-cured product and the photo-cured/thermally cured product described below becomes insufficient.
- the addition amount is more than 20 mass %, a large part of light radiated to the photo-curable composition is absorbed by the photo-radical generator (c), which exists excessively, and the light may not reach an inside of the curable composition. Therefore, there is a risk in that the polymerization conversion rate of the photo-curable composition in the inside thereof is reduced.
- the photo-curable composition according to this embodiment may further include a reactive diluent (d).
- a reactive diluent (d) When the reactive diluent (d) is incorporated in the photo-curable composition, the viscosity of the photo-curable composition can be reduced.
- the mechanical characteristics and the thermal characteristics of the photo-cured product and the photo-cured/thermally cured product described below can be controlled.
- the reactive diluent (d) is preferably a monomer and/or oligomer having a radically and/or cationically polymerizable group.
- Examples of the monomer having a radically polymerizable group include a (meth)acrylate-based monomer, a styrene-based monomer, acrylonitrile, a vinyl ester-based monomer, N-vinylpyrrolidone, an acrylamide-based monomer, a conjugated diene-based monomer, a vinyl ketone-based monomer, and a vinyl halide- or vinylidene halide-based monomer.
- Examples of the monomer having a cationically polymerizable group include an epoxy-based monomer, an oxetane-based monomer, and a vinyl ether-based monomer.
- a (meth)acrylate-based monomer having the (meth)acryloyl group same as in the blocked isocyanate (a) out of the monomers each having a radically polymerizable group is preferred.
- the (meth)acrylate-based monomer may include a monofunctional (meth)acrylate, a difunctional (meth)acrylate, a tri- or more functional (meth)acrylate, a urethane (meth)acrylate oligomer, and a polyester (meth)acrylate oligomer.
- Examples of the (meth)acrylate-based monomer include: monofunctional (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth
- urethane (meth)acrylate oligomer examples include, but are not limited to, a polycarbonate-based urethane (meth)acrylate, a polyester-based urethane (meth)acrylate, a polyether-based urethane (meth)acrylate, and a caprolactone-based urethane (meth)acrylate.
- the urethane (meth)acrylate oligomer may be obtained by, for example, subjecting an isocyanate compound, which is obtained through a reaction between a polyol and a diisocyanate, and a (meth)acrylate monomer having a hydroxyl group to a reaction.
- the polyol examples include a polycarbonate diol, a polyester polyol, a polyether polyol, and a polycaprolactone polyol.
- the polyester acrylate oligomer is obtained by, for example, obtaining a polyester oligomer having hydroxyl groups at both ends thereof through condensation between a polycarboxylic acid and a polyol, and then esterifying the hydroxyl groups at both the ends with acrylic acid.
- the reactive diluent (d) may be added in an appropriate amount as long as the effects of the present invention are not impaired so that desired values for the viscosity and the curing speed of the photo-curable composition, and desired values for the mechanical and thermal characteristics of the cured product are obtained.
- the photo-curable composition according to this embodiment may further include a photoacid generator (e) when the photo-curable composition includes the monomer or oligomer having a cationically polymerizable group as the reactive diluent (d).
- a photoacid generator e
- the photoacid generator (e) include, but are not limited to, a trichloromethyl-s-triazine, a sulfonium salt, an iodonium salt, a quaternary ammonium salt, a diazomethane compound, an imidosulfonate compound, and an oxime sulfonate compound.
- the photo-curable composition according to this embodiment may include, as required, one kind or two or more kinds of additives selected from, for example, a colorant, such as a pigment or a dye, a defoamer, a leveling agent, a thickener, a flame retardant, an antioxidant, an inorganic filler (cross-linked polymer particles, silica, glass powder, ceramics powder, metal powder, or the like), and a modifier resin (a thermoplastic resin, thermoplastic resin particles, rubber particles, or the like) in an appropriate amount.
- a colorant such as a pigment or a dye, a defoamer, a leveling agent, a thickener, a flame retardant, an antioxidant, an inorganic filler (cross-linked polymer particles, silica, glass powder, ceramics powder, metal powder, or the like)
- a modifier resin a thermoplastic resin, thermoplastic resin particles, rubber particles, or the like
- the photo-curable composition according to this embodiment may include, as required, in addition to the photo-radical generator (c), a photoinitiation auxiliary or a sensitizer.
- a photoinitiation auxiliary or the sensitizer include, but are not limited to, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound.
- a resin (photo-cured product) according to a third embodiment of the present invention is described.
- the resin (photo-cured product) according to this embodiment is a resin in a solid state obtained by irradiating the photo-curable composition according to the second embodiment with an active energy ray, such as light having a predetermined wavelength.
- the resin (photo-cured product) according to this embodiment includes a repeating structural unit represented by the following general formula (4).
- R 5 , R 9 , R 10 , and R 11 each independently represent a hydrogen atom or a methyl group
- R 12 , R 13 , R 14 , and R 15 each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- L 2 , L 3 , L 4 , and L 5 each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- R 16a , R 16b , R 17 , R 18 , R 19 , and R 20 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
- Y 2 represents a divalent linking group
- “b” represents an integer of 1 or more and 99 or less.
- the substituent may be a substituent including a carbon atom.
- an atom of the substituent which is bonded to each of L 2 , L 3 , L 4 , L 5 , R 3a , R 13 , R 14 , R 15 , R 16a , R 16b , R 17 , R 18 , R 19 , and R 20 is an atom other than the carbon atom.
- the number of carbon atoms included in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.
- R 12 , R 13 , R 14 , and R 15 each preferably represent a group selected from the group consisting of a tert-butyl group, a tert-pentyl group, and a tert-hexyl group.
- L 2 , L 3 , L 4 , and L 5 each preferably represent an ethylene group or a propylene group.
- Y 2 preferably represents at least one divalent linking group selected from the group consisting of groups represented by the formulae (B1) to (B3).
- the active energy ray to be radiated to the photo-curable composition is not particularly limited as long as the active energy ray can cure the photo-curable composition according to this embodiment.
- Specific examples of the active energy ray include: electromagnetic waves, such as an ultraviolet ray, visible light, an infrared ray, an X-ray, a gamma ray, and laser light; and particle beams, such as an alpha ray, a beta ray, and an electron beam.
- an ultraviolet ray is most preferred in terms of an absorption wavelength of the photo-radical generator (c) to be used and facility introduction cost.
- An exposure amount is not particularly limited, but is preferably 0.001 J/cm2 or more and 10 J/cm2 or less. When the exposure amount is less than 0.001 J/cm2, there is a risk in that the photo-curable composition is not cured sufficiently. When the exposure amount is more than 10 J/cm2, an irradiation time period is prolonged, and productivity is reduced.
- the photo-curable composition according to this embodiment can be suitably used for a method of manufacturing a three-dimensional object by stereolithography.
- a method of manufacturing a three-dimensional object including using the photo-curable composition according to this embodiment is described below.
- the method of manufacturing a three-dimensional object according to this embodiment is a method including repeatedly performing a step of curing the photo-curable composition according to this embodiment layer by layer by selectively radiating the active energy ray, such as light, to the photo-curable composition, to thereby manufacture a three-dimensional object.
- the active energy ray is selectively radiated to the photo-curable composition based on slice data of a three-dimensional object to be created.
- a method of radiating the active energy ray to the photo-curable composition is not particularly limited.
- the following methods may be adopted.
- As a first method there is given a method involving using light focused to a spot, such as laser light, and two-dimensionally scanning the photo-curable composition with the light. In this case, the two-dimensional scanning may be performed in a point drawing mode or a line drawing mode.
- the active energy ray may be radiated in a planar manner through a planar drawing mask formed by arranging a plurality of micro light shutters, such as liquid crystal shutters or digital micro mirror shutters.
- a surface of the obtained three-dimensional object may be washed with a washing agent, such as an organic solvent.
- the obtained three-dimensional object may be subjected to post-curing involving irradiating the three-dimensional object with light to cure a residual component, which may remain unreacted on the surface or in the inside of the three-dimensional object.
- a resin (photo-cured/thermally cured product) according to a fourth embodiment of the present invention is described.
- the resin (photo-cured/thermally cured product) according to this embodiment is a resin in a solid state obtained by subjecting the resin (photo-cured product) according to the third embodiment to heat treatment.
- the resin (photo-cured/thermally cured product) according to this embodiment includes a repeating structural unit represented by the following general formula (5) and a repeating structural unit represented by the following general formula (6).
- R 21 represents a hydrogen atom or a methyl group
- R 22 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- L 6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
- L 7 , L 5 , L 9 , and L 10 each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent
- R 23a , R 23b , R 24 , R 25 , R 26 , and R 27 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
- Y 3 represents a divalent linking group
- c represents an integer of 1 or more and 99 or less
- X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 each independently represent any one of O, S, and NH.
- the substituent may be a substituent including a carbon atom.
- an atom of the substituent which is bonded to each of L 6 , L 7 , L 8 , L 9 , L 10 , R 22 , R 23a , R 23b , R 24 , R 25 , R 26 , and R 27 is an atom other than the carbon atom.
- the number of carbon atoms included in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.
- R 22 preferably represents a group selected from the group consisting of a tert-butyl group, a tert-pentyl group, and a tert-hexyl group.
- L 6 , L 7 , L 5 , L 9 , and L 10 each preferably represent an ethylene group or a propylene group.
- Y 3 preferably represents at least one divalent linking group selected from the group consisting of groups represented by the formulae (B1) to (B3).
- FIG. 1 s a view for illustrating a reaction scheme in which the photo-curable composition according to the second embodiment is irradiated with light to provide the resin (photo-cured product) according to the third embodiment, and then the resin (photo-cured product) is subjected to heat treatment to provide the resin (photo-cured/thermally cured product) according to the fourth embodiment.
- the photo-curable composition includes: the blocked isocyanate (a); the chain extender (b); and the photo-radical generator (c).
- the photo-radical generator (c) in the photo-curable composition When the photo-curable composition according to this embodiment illustrated in (A) of FIG. 1 s irradiated with light (e.g., ultraviolet ray) having a predetermined wavelength, the photo-radical generator (c) in the photo-curable composition generates a radical. Then, the (meth)acryloyl groups of the blocked isocyanate (a) are subjected to a polymerization reaction, and thus the photo-curable composition is solidified.
- the photo-curable composition further includes the reactive diluent (d) described above, not only a polymerization reaction between the blocked isocyanates (a), but also a polymerization reaction between the blocked isocyanate (a) and the reactive diluent (d) proceeds. With this, a photo-cured product as schematically illustrated in (B) of FIG. 1 s generated.
- a cured product obtained through a polymerization reaction of polyfunctional (meth)acryloyl groups tends to have a high crosslinking density and low toughness.
- the deblocking occurs as described above when the photo-curable composition having been photo-cured is subjected to heat treatment.
- a crosslinking density obtained through crosslinking in association with the (meth)acryloyl groups is reduced.
- the urethane bond or the urea bond is generated, and thus a cured product having a polyurethane structure, a polyurea structure, or a mixed structure thereof is generated.
- the cured product having a polyurethane structure, a polyurea structure, or a mixed structure thereof has, in a molecular structure thereof, at least four blocking groups, that is, four crosslinking points. Therefore, the cured product has a high crosslinking density, and as a result, can have a higher modulus of elasticity and higher toughness than a related-art cured product.
- a compound was identified by dissolving 15 mg of a sample in 1.1 g of deuterated chloroform (CDCl3), and subjecting the resultant solution to 1 H-NMR measurement with a nuclear magnetic resonance spectrometer JNM-ECA-400 (manufactured by JEOL Ltd.).
- a sample was measured by an attenuated total reflection method (ATR method) with a Fourier transform infrared spectrometer (Spectrum One manufactured by PerkinElmer, Inc.). An absorbance was plotted on the ordinate, and the proceeding of a reaction was confirmed based on the presence or absence of a peak around 2,260 cm ⁇ 1 derived from an isocyanate group.
- a test piece was produced by punching a cured product having a thickness of about 300 ⁇ m into a No. 8 dumbbell shape. The test piece was measured for a tensile strength and a tensile modulus of elasticity at a test temperature of 23° C. and a tension speed of 10 mm/min with a tensile tester (product name “Strograph EII”, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in conformity with JIS K 7127.
- a Charpy impact strength was measured under an atmosphere of 23° C. with an impact tester (product name “digital impact tester DG-UB”, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in conformity with JIS K 7111.
- test piece to be used was obtained as described below.
- a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was produced from a cured product, and a notch having a depth of 2 mm and an angle of 45° was formed in a middle portion of the test piece.
- a blocked isocyanate 1 was synthesized.
- polytetrahydrofuran 100 g, 154 mmol, 1.0 eq.
- hexamethylene diisocyanate 207 g, 1.23 mol, 8.0 eq.
- Tin(II) 2-ethylhexanoate 80 ⁇ L, cat.
- a blocked isocyanate 2 was synthesized.
- polytetrahydrofuran 100 g, 154 mmol, 1.0 eq.
- hexamethylene diisocyanate 53.5 g, 615 mmol, 4.0 eq.
- Tin(II) 2-ethylhexanoate 80 ⁇ L, cat.
- the solution was stirred at room temperature for 5 hours.
- the solution was added to hexane (4 L) vigorously stirred.
- the blocked isocyanate 1 and/or the blocked isocyanate 2 serving as a blocked isocyanate, 4,4′-diaminodiphenylmethane serving as a chain extender, isobornyl methacrylate serving as a reactive diluent, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide serving as a photo-radical generator in amounts shown in Table 1 were loaded in a light shielding bottle, and stirred to uniformity with a stirring deaerator. Thus, each of photo-curable compositions 1 to 4 was prepared.
- Each of the photo-curable compositions 1 to 4 was poured between two quartz glass sheets between which a gap was formed with a 300 ⁇ m spacer.
- An ultraviolet ray at 5 mW/cm2 was radiated to each of the photo-curable compositions 1 to 4 for 120 seconds with an ultraviolet ray irradiation device (manufactured by Hoya-Schott Corporation, product name, UV Light Source EX250).
- an ultraviolet ray irradiation device manufactured by Hoya-Schott Corporation, product name, UV Light Source EX250.
- Each of the photo-curable compositions 1 to 4 was poured into a mold measuring 80 mm ⁇ 10 mm ⁇ 4 mm which was sandwiched between glasses from both surfaces thereof.
- An ultraviolet ray at 5 mW/cm2 was first radiated to both surfaces for 120 seconds per surface, and was then radiated thereto for 360 seconds per surface with an ultraviolet ray irradiation device (manufactured by Hoya-Schott Corporation, product name, UV Light Source EX250).
- an ultraviolet ray irradiation device manufactured by Hoya-Schott Corporation, product name, UV Light Source EX250.
- Each of the photo-cured products 1 to 4 was placed in an oven at 125° C. and subjected to heat treatment for 4 hours. Thus, each of photo-cured/thermally cured products 1 to 4 was obtained.
- the tensile modulus of elasticity, the tensile strength, and the Charpy impact strength of each of the photo-cured/thermally cured products 1 to 4 were measured by the above-mentioned methods. The results are shown in Examples 1 to 4 of Table 1.
- the photo-cured/thermally cured products each having a higher modulus of elasticity, higher tensile strength, and higher Charpy impact strength than the photo-cured/thermally cured product formed with the photo-curable composition of Comparative Example were able to be formed.
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
wherein, in the general formula (1), A1 to A4 each independently represent a structure represented by the following general formula (2), and B represents a structure represented by the following general formula (3)
Description
in the general formula (1), A1 to A4 each independently represent a structure represented by the following general formula (2), and B represents a structure represented by the following general formula (3);
in the general formula (2), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and L1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent;
in the general formula (3), R3a, R3b, R4, R5, R6, and R7 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, Y1 represents a divalent linking group, and “a” represents an integer of 1 or more and 99 or less.
in the general formula (1), A1 to A4 each independently represent a structure represented by the following general formula (2), and B represents a structure represented by the following general formula (3);
in the general formula (2), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and L1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent;
in the general formula (3), R3a, R3b, R4, R5, R6, and R7 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, Y1 represents a divalent linking group, and “a” represents an integer of 1 or more and 99 or less.
TABLE 1 | |||
Result of tensile test | Result of impact |
Composition of photo-curable composition | Modulus | strength test |
Photo- | of | Tensile | Charpy impact | |
polymerization | elasticity | strength | strength |
Blocked isocyanate | Chain extender | Reactive diluent | initiator | Gpa | Mpa | kJ/m2 | ||
Example 1 | Blocked | Blocked | 4,4′- | Isobornyl | Bis(2,4,6- | 0.66 | 28.3 | 7.3 |
isocyanate 1 | isocyanate 2 | Diaminodiphenylmethane | methacrylate | trimethylbenzoyl)- | ||||
10.7 parts | 42.7 parts | 6.2 parts by weight | 39.7 parts | phenylphosphine | ||||
by weight | by weight | by weight | oxide 0.7 part by | |||||
weight | ||||||||
Example 2 | Blocked | Blocked | 4,4′- | Isobornyl | Bis(2,4,6- | 0.92 | 31.4 | 6.6 |
isocyanate 1 | isocyanate 2 | Diaminodiphenylmethane | methacrylate | trimethylbenzoyl)- | ||||
26.7 parts | 26.7 parts | 6.2 parts by weight | 39.7 parts | phenylphosphine | ||||
by weight | by weight | by weight | oxide 0.7 part by | |||||
weight | ||||||||
Example 3 | Blocked | Blocked | 4,4′- | Isobornyl | Bis(2,4,6- | 1.03 | 37.5 | 6.4 |
isocyanate 1 | isocyanate 2 | Diaminodiphenylmethane | methacrylate | trimethylbenzoyl)- | ||||
40.1 parts | 13.3 parts | 6.2 parts by weight | 39.7 parts | phenylphosphine | ||||
by weight | by weight | by weight | oxide 0.7 part by | |||||
weight | ||||||||
Example 4 | Blocked | Blocked | 4,4′- | Isobornyl | Bis(2,4,6- | 1.21 | 38.8 | 6.7 |
isocyanate 1 | isocyanate 2 | Diaminodiphenylmethane | methacrylate | trimethylbenzoyl)- | ||||
53.4 parts | 0 parts | 6.2 parts by weight | 39.7 parts | phenylphosphine | ||||
by weight | by weight | by weight | oxide 0.7 part by | |||||
weight | ||||||||
Comparative | Blocked | Blocked | 4,4′- | Isobornyl | Bis(2,4,6- | 0.45 | 21.3 | 1.0 |
Example 1 | isocyanate 1 | isocyanate 2 | Diaminodiphenylmethane | methacrylate | trimethylbenzoyl)- | |||
0 parts | 53.4 parts | 6.2 parts by weight | 39.7 parts | phenylphosphine | ||||
by weight | by weight | by weight | oxide0.7 part by | |||||
weight | ||||||||
Claims (10)
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JP2017-226771 | 2017-11-27 | ||
JP2017226771A JP7066384B2 (en) | 2017-11-27 | 2017-11-27 | Methods for Producing Blocked Isocyanates, Photocurable Compositions, Resins, and Three-dimensional Objects |
JPJP2017-226771 | 2017-11-27 |
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US20190161573A1 US20190161573A1 (en) | 2019-05-30 |
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CN115215751B (en) * | 2022-08-15 | 2024-02-02 | 万华化学集团股份有限公司 | Preparation and application of tertiary amine catalyst and organic metal-tertiary amine complex catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015200189A1 (en) | 2014-06-23 | 2015-12-30 | Carbon3D, Inc. | Three-dimensional objects produced from materials having multiple mechanisms of hardening |
WO2017112653A1 (en) | 2015-12-22 | 2017-06-29 | Carbon, Inc. | Dual precursor resin systems for additive manufacturing with dual cure resins |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015200189A1 (en) | 2014-06-23 | 2015-12-30 | Carbon3D, Inc. | Three-dimensional objects produced from materials having multiple mechanisms of hardening |
WO2015200201A1 (en) | 2014-06-23 | 2015-12-30 | Carbon3D, Inc. | Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects |
WO2015200179A1 (en) | 2014-06-23 | 2015-12-30 | Carbon3D, Inc. | Methods of producing polyurethane three-dimensional objects from materials having multiple mechanisms of hardening |
WO2015200173A1 (en) | 2014-06-23 | 2015-12-30 | Carbon3D, Inc. | Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening |
JP2017524565A (en) | 2014-06-23 | 2017-08-31 | カーボン,インコーポレイテッド | Polyurethane three-dimensional object manufacturing method from materials with various curing mechanisms |
JP2017527637A (en) | 2014-06-23 | 2017-09-21 | カーボン,インコーポレイテッド | Polyurethane resin with various curing mechanisms used in the production of three-dimensional objects |
WO2017112653A1 (en) | 2015-12-22 | 2017-06-29 | Carbon, Inc. | Dual precursor resin systems for additive manufacturing with dual cure resins |
Non-Patent Citations (1)
Title |
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Notice of Reasons for Refusal in Japanese Application No. 2017-226771 (dated Sep. 2021). |
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